Phenyl-azo-tetrahydroquinoline azo compounds

ABSTRACT

Azo compounds especially useful for dyeing polyamide fibers on which the compounds exhibit improved fastness and dyeability properties contain a phenyl diazo component having a substituent in the 4-position and hydrogen, chlorine or bromine in the 2-position, and a tetramethyl substituted tetrahydroquinoline coupling component.

This is a continuation-in-part application of our copending applicationSer. No. 216,239 filed Jan. 7, 1972, now abandoned.

This invention concerns certain novel azo compounds especially usefulfor dyeing polyamide fibers, yarns and fabrics. These azo compounds havethe general formula ##SPC1##

Wherein

R¹ is hydrogen, halogen or cyano;

R² is lower alkylsulfonyl; lower alkylsulfonyl substituted with cyano,hydroxy, cyclohexyl or aryl; lower alkoxycarbonyl; lower alkoxycarbonylsubstituted with lower alkoxy, lower alkanoyloxy, cyano, halogen oraryl; cyano; --SO₂ NR⁹ R¹⁰ ; --CONR⁹ R¹⁰ ; or arylazo;

R³ is hydrogen or halogen;

R⁴ is methyl or, when R⁵ and R⁶ each is hydrogen, R⁴ can be lower alkyl;

R⁵ and R⁶ each is hydrogen or methyl;

R⁷ is hydrogen or lower alkyl; and

R⁸ is alkyl containing one to about eight carbon atoms or lower alkylsubstituted with hydroxy, --CONR⁹ R¹⁰ or ##EQU1## in which R⁹individually is hydrogen, lower alkyl, cyclohexyl or aryl; R¹⁰individually is hydrogen or lower alkyl; R⁹ and R¹⁰ in combination arepentamethylene or ethyleneoxyethylene; R¹¹ is hydrogen, lower alkyl orlower hydroxyalkyl; R¹² is aryl, cyclohexyl, furyl, lower alkyl or loweralkyl substituted with hydroxy, lower alkoxy, cyano, halogen, aryl oraryloxy; X is --CO--, --COO-- or --SO₂ --; and each aryl moiety isphenyl or phenyl substituted with lower alkyl, lower alkoxy or halogen.

Our novel azo compounds exhibit good dyeability, as exemplified bysuperior exhaustion, good color fastness to perspiration (acid),superior dry heat fastness, migration, fastness to light, and resistanceto sublimation when applied to polyamide fibers by conventionaaldisperse dyeing techniques. Another advantage inherent in our novelcompounds is their relatively low cost. This excellent combination ofproperties renders the novel compounds superior to knownphenyl-azo-tetrahydroquinoline compounds such as those disclosed in U.S.Pat. Nos. 2,251,947; 2,261,176; 2,322,925; 2,323,315; 2,342,678;2,351,886; 2,442,345; 2,338,871 and 3,386,990. Our azo compounds areespecially valuable for dyeing carpets of polyamide fibers wherefastness to light and migration are particularly important.

The substituents represented by R¹ through R⁸ are well known in the artand/or can be derived from commercially-available or readily-obtainablechemicals by means of published procedures. As used herein to describean alkyl moiety, "lower" designates a carbon content of one to aboutfour carbon atoms, e.g., methyl, ethyl, propylene, isopropyl, butyl andisobutyl. Chlorine and bromine are typical of the halogen atoms whichcan be present on our novel azo compounds. The alkylsulfonyl andalkoxycarbonyl groups which R² can represent preferably areunsubstituted. Preferred groups represented by R⁸ are lower alkyl or thegroup having the formula --(CH₂)_(n) -- Y in which n is two or three andY is hydroxy, --CONR⁹ R¹⁰ or --NH--X--R¹² in which R⁹ and R¹⁰ each ishydrogen or lower alkyl or, in combination, R⁹ and R¹⁰ arepentamethylene or ethyleneoxyethylene, X is --CO-- or --COO-- and R¹² isphenyl, cyclohexyl, lower alkyl or lower alkyl substituted with hydroxy,lower alkoxy, cyano, chlorine, bromine, phenyl or phenoxy.

A group of our novel compounds which, because of their relative economyand excellent properties, are especially valuable for dyeing polyamidefibers having the formula ##SPC2##

wherein

R¹ is hydrogen, chlorine or bromine;

R² is lower alkylsulfonyl, lower alkoxycarbonyl, cyano, --SO₂ NR⁹ R¹⁰,or --CONR⁹ R¹⁰ ; and

R⁸ is lower alkyl, --CH₂ CH₂ CONR⁹ R¹⁰, or --(CH₂)_(n) --NH--X--R¹² ; inwhich R⁹ and R¹⁰ each is hydrogen or lower alkyl or, in combination, R⁹and R¹⁰ are pentamethylene or ethyleneoxyethylene, n is two or three, Xis --CO-- or --COO--, and R¹² is lower alkyl.

The novel compounds of the invention are prepared by diazotizing anappropriately substituted aniline compound and coupling the resultingdiazonium salt with a coupler having the formula ##SPC3##

according to conventional procedures. The aniline compounds are knownand/or can be obtained according to published techniques. The couplers(II) also can be synthesized by means well known in the art. Forexample, an N-cyanoalkyl-1,2,3,4,-tetrahydroquinoline can be hydrolyzedto form the corresponding N-carbamoylakyl compound or it can becatalytically hydrogenated to the corresponding aminoalkyl compoundwhich then can be treated with a variety of acylating agents to yieldthe N-acylamidoalkyl-1,2,3,4-tetrahydroquinoline coupler. Additionalprocedures are disclosed in U.S. Pat. Nos. 3,247,211 and 3,254,073.

Our novel azo compounds and their synthesis are further illustrated bythe following examples.

EXAMPLES 1-10

To 50 ml. of concentrated H₂ SO₄ is added 7.2 g. NaNO₂ portionwise withstirring. The solution is cooled and 100 ml. of 1:5 acid (1 partpropionic acid; 5 parts acetic acid) is added below 20°C. The mixture iscooled and 2-bromo-4-cyanoaniline (19.7 g.) is added, followed by 100ml. 1:5 acid, all below 5°C. The reaction is stirred at 0-5°C. for 2 hr.Each of the following couplers (.01 mole) is dissolved in a 40 ml.portion of 1:5 acid.

N-(2-Carbamoylethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline(Example 1).

N-(2-Acetamidoethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline(Example 2).

N-(3-Acetamidopropyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline(Example 3).

N-(3-Ethoxy carbonylaminopropyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline (Example4).

N-(2-Hydroxyethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline(Example 5).

N-(2-Propionamidoethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline(Example 6).

N-(2-Carbamoylethyl)-2,7-dimethyl-1,2,3,4-tetrahydroquinoline (Example7).

N-(2-Acetamidoethyl)-2,7-dimethyl-1,2,3,4-tetrahydroquinoline (Example8).

N-(2-Carbamoylethyl)-2-isopropyl-7-methyl-1,2,3,4,-tetrahydroquinoline(Example 9).

N-(2-Carbamoylethyl)-2,24-trimethyl-1,2,3,4-tetrahydroquinoline (Example10).

To each chilled coupler solution is a .01 mole aliquot of diazoniumsolution. The coupling mixtures are buffered by the addition of ammoniumacetate and allowed to stand for 1 hr. The azo products are precipitatedby the addition of water, collected by filtration, washed with water,and dried in air. If necessary, the azo products can be purified byslurrying in hot methanol, cooling, filtering, and washing withmethanol. Each of the azo compounds obtained produces bright, level redshades on polyamide fibers and exhibits good fastness to light.

The azo compounds set forth in the examples of the following Tableconform to Formula (I) and are prepared according to the proceduresdescribed hereinabove. Examples 1-10 of the Table designate thestructures of the azo compounds prepared in Examples 1-10 above. Thecolor given for each compound refers to the shade it produces onpolyamide fibers.ExampleNo. R¹ R² R³ R⁴,R⁵,R⁶,R⁷ R⁸Color__________________________________________________________________________1 --Br --CN H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Red 2 --Br --CN H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₃ Red 3 --Br --CN H 2,2,4,7-tetra-CH₃--(CH₂)₃ NHCOCH_(HCOCH).su b.3 Red 4 --Br --CN H 2,2,4,7-tetra-CH₃--(CH₂)₃ NHCOOC₂ H₅ Red 5 --Br --CN H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Red6 --Br --CN H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOC₂ H₅ Red 7 --Br --CN H2,7-di-CH₃ --CH₂ CH₂ CONH₂ Red 8 --Br --CN H 2,7-di-CH₃ --CH₂ CH₂NHCOCH₃ Red 9 --Br --CN H 2-CH(CH₃)₂ --7-CH₃ -- CH₂ CH₂ CONH₂ Red10 --Br--CN H 2,2,4-tri-CH₃ --CH₂ CH₂ CONH₂ Red11 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Red12 Cl --SO₂ (CH₂)₃ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Red13 Cl --SO₂ CH₂ CH₂ CN H2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Red14 Cl --SO₂ CH₃ C₆ H₁₁ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Red15 Cl --SO₂ CH₂ CH₂ C₆ H₅ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Red16 Br --SO₂ CH₃ H 2,2,4,7-tetra-CH₃--CH₂ CH₂ OH Red17 Br --SO₂ CH₃ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂Red18 Cl --SO₂ CH₃ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Red19 Cl --SO₂CH₃ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₃ Red20 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₃ Red21 Cl --SO₂ CH₃ H 2,7-di-CH₃ --CH₂CH₂ NHCOC₂ H₅ Red22 Cl --SO₂ CH₃ H 2,2,4,7-tetra-CH₃ --CH₂ CH(CH₃)₂Red23 Cl --SO₂ CH₃ H 2,2,4,7-tetra-CH₃ --CH₂ CH(C₂ H₅)(CH.sub. 2)₃ CH₃Red24 Cl --SO₂ CH₃ H 2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₂ Red25 Cl --SO₂CH₃ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOOC₂ H₅ Red26 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --(CH₂)₃ NHSO₂ CH₃ Red27 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOC₆ H₁₁ Red28 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOC₆ H₅ Red29 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₂ Red30 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₂ CH₂ OCH₃ Red31 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONHC₂ H₅ Red32 Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONHCH(CH₃).s ub.2 Red33 Cl --SO₂ CH₃ --Cl2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Reddish-brown34 --CN --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₃ Violet35 --CN --CN H2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₃ Violet36 --CN --COOC₂ H₅ H2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₃ Violet37 --CN --SO₂ NHC₂ H₅ H2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₃ Violet38 H --CN H 2,2,4,7-tetra-CH₃--(CH₂)₃ NHCOCH₃ Orange39 H --SO₂ CH₃ H 2,2,4,7-tetra-CH₃ --(CH₂)₃NHCOCH₃ Orange40 --Cl --CN H 2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₃ Red41--Br --COOC₂ H₅ H 2,2,4,7-tetra-CH₃ --(CH₂)₃ NHCOCH₃ Red42 --Br -- COOC₂H₅ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Red43 --Br --COOC₂ H₅ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₃ Red44 --Br --CN H 2,2,4,7-tetra-CH₃--CH₂ CH₂ N(CH₂ H₂ OH)SO₂ CH₃ Red45 --Br --CONH₂ H 2,2,4,7-tetra-CH₃--CH₂ CH₂ CONH₂ Scarlet46 --Br --CONH₂ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ OHScarlet47 --Br --CONH₂ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₃ Scarlet48--Br --CONH₂ H 2,2,4,7-tetra-CH₃ --C₂ H₅ Scarlet49 --Br --CONHC₂ H₅ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Scarlet50 --Br --CON(C₂ H₅)₂ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Scarlet51 --Br --CONHC₆ H₅ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Scarlet52 --Br --CONHC₆ H₁₁ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Scarlet53 --CN --CONH₂ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Red54 --Br --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH(OH)CH₃ Red55 --Br --SO₂ NHC₂ H₅ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Scarlet56 --Br --SO₂ NCH₂ CH₂ OCH₂ CH₂H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Scarlet57 --Br --SO₂ CH₃ H2,2,4-tri-CH₃ --CH₂ CH₂ CONH₂ Red58 --Br --CN H 2-CH(CH₃)₂ -7-CH₃ --CH₂CH₂ OH Red59 --Br --SO₂ CH₂ CH₂ OH H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ OHRed60 --Br --SO₂ CH₂ CN H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Red61 --Br--COOCH₃ H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ OH Scarlet62 --Cl --CONH₂ --Cl2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₃ Reddish-brown63 --Cl --SO₂ CH₃ --Br2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₃ Reddish-brown64 --Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₂ CH₂ Cl Red65 --Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₂ OC₆ H₅ Red66 --Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCO(CH₂).sub .3 OH Red67 --Cl --SO₂ CH₃ H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONHCH₂ CH₂ CH₂ CH₂ CH₂ Red68 H C₃ H₅ N=N--H 2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOCH₃ Red69 H p-CH₃ O--C₃ H₄ N=N-- H2,2,4,7-tetra-CH₃ --CH₂ CH₂ CONH₂ Red70 H o-Cl-p-CH₃ --C₆ H₅ N=N-- H2,2,4,7-tetra-CH₃ --CH₂ CH₂ NHCOOC₂ H₅Red__________________________________________________________________________

The novel azo compounds can be applied to polyamide textile materials,including yarns, fabrics and carpets, according to known disperse dyeingtechniques. Various dispersing and wetting agents can be employed in thedispersion of the finely divided dye compound in an essentially aqueousdyebath. Procedures by which the compounds of the invention can beapplied to polyamide textile materials are described in U.S. Pat. Nos.3,100,134 and 3,320,021. The following example illustrates a method forapplying the novel compounds to polyamide fibers.

EXAMPLE 71

The azo compound (16.7 mg.) of Example 1 is dispersed in 10 cc. of2-methoxyethanol. A small amount (3-5 cc.) of a 3% sodium ligninsulfonate solution is added, with stirring, and then the volume of thebath is brought to 150 cc. with water. A 5 g. textile fabric made ofnylon 66 fibers is placed in the bath and worked 10 minutes withoutheat. The bath is then slowly brought to the boil over a 30-minuteperiod and the dyeing is carried out at the boil for one hour. The dyedfabric is then removed from the dyebath, rinsed with water and dried inan oven at 250°F. The fabric is dyed a bright shade of red exhibitingexcellent fastness properties when tested in accordance with theprocedures described in the Technical Manual of the American Associationof Textile Chemists and Colorists, 1968 edition.

The polyamide materials which can be dyed with the novel azo compoundsare well known and include nylon 66 (polyhexamethylene adipamide)manufactured by the polymerization of adipic acid andhexamethylenediamine, nylon 6 (polycaprolactum) prepared fromepsilon-aminocaproic acid lactum (caprolactum) and nylon 8. A detaileddescription of the synthetic polyamide materials which are dyed bright,fast shades by the compounds of the invention is set forth in U.S. Pat.No. 3,100,134. Although our novel compounds are particularly suited fordyeing polyamide fibers, they also can be used to dye other synthetictextile materials such as cellulose acetate and polyamide fibers.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A compound having the formula ##SPC4##wherein R¹ ishydrogen, chlorine, or bromine; R² is lower alkylsulfonyl, loweralkoxycarbonyl, cyano, --SO₂ NR⁹ R¹⁰, or --CONR⁹ R¹⁰ ; R⁸ is lower alkylor the group --(CH₂)_(n) -- Y in which n is two or three and Y ishydroxy, --CONR⁹ R¹⁰ or --NH--X--R¹² ; in which R⁹ and R¹⁰ individuallyare hydrogen or lower alkyl, R⁹ and R¹⁰ in combination arepentamethylene or ethyleneoxyethylene, X is --CO-- or --COO--, and R¹²is phenyl, cyclohexyl, lower alkyl or lower alkyl substituted withhydroxy, lower alkoxy, cyano, chlorine, bromine, phenyl or phenoxy.
 2. Acompound according to claim 1 having the formula ##SPC5##wherein R¹ ishydrogen, chlorine or bromine; R² is lower alkylsulfonyl, loweralkoxycarbonyl, cyano, --SO₂ NR⁹ R¹⁰, or --CONR⁹ R¹⁰ ; and R⁸ is loweralkyl, --CH₂ CH₂ CONR⁹ R¹⁰, or --(CH₂)_(n) --NH--X--R¹² ; in which R⁹and R¹⁰ individually are hydrogen or lower alkyl, R⁹ and R¹⁰ incombination are pentamethylene or ethyleneoxyethylene, n is two orthree, X is --CO-- or --COO--, and R¹² is lower alkyl.
 3. A compoundaccording to claim 1 having the formula ##SPC6##
 4. A compound accordingto claim 1 having the formula ##SPC7##
 5. A compound according to claim1 having the formula ##SPC8##
 6. A compound according to claim 1 havingthe formula ##SPC9##
 7. A compound according to claim 1 having theformula ##SPC10##
 8. A compound according to claim 1 having the formula##SPC11##
 9. A compound according to claim 1 having the formula##SPC12##
 10. A compound according to claim 1 having the formula##SPC13##